JP6661534B2 - Reaction product production method using phase interface reaction, phase interface reaction device, and secondary reaction product production method - Google Patents

Description

Cross reference

  This application claims priority based on Japanese Patent Application No. 2014-132690 filed on June 27, 2014 in Japan, and the contents described in the application are incorporated herein by reference. The contents described in the patents, patent applications, and documents cited in the present application are incorporated herein by reference.

  The present invention provides a method for producing a reaction product and a phase interface reaction device using a phase interface reaction in which a reaction occurs at a phase interface between a plasma phase and a liquid phase in contact with the plasma phase, and a method for producing a secondary reaction product. About.

When oxygen molecules are allowed to pass through the discharge space, ozone is generated by the conversion of oxygen to plasma, and when ultraviolet light is applied to the ozone, hydroxy radicals and the like are generated. Water purifiers utilizing this principle and high oxidizing power such as hydroxyl radicals have been developed (see Patent Documents 1 and 2). The generation of hydroxy radical from ozone proceeds according to the following reaction formulas (1) and (2).
O ₃ + hν (UV) → ³ O ₂ + O (1)
O + H ₂ O + hν (UV) → 2HO · (2)

  Here, in the water purification device, water molecules (water vapor) contained in the air react with oxygen atoms to form hydroxy radicals (the above formula (2)). The proportion of water vapor contained in the air is at most about 3 or 4% by volume, and a large amount of hydroxyl radical cannot be generated. Although it is conceivable to generate ozone (plasma) in a high humidity state, discharge is not efficiently performed in a high humidity state, and ozone cannot be generated sufficiently.

  On the other hand, ammonia is important as a raw material for nitrogen fertilizer, urea and the like, and as an industrial production method, the Haber-Bosch method is famous. This method is a method in which nitrogen and hydrogen are reacted under high temperature and high pressure using an iron-based catalyst to synthesize ammonia. Hydrogen, which is one of the raw materials for ammonia synthesis, is usually obtained by steam reforming of a buried hydrocarbon represented by petroleum, coal or natural gas. For these reasons, the Haber-Bosch method is a heavy and long reaction method that requires enormous energy, and is a reaction method that generates a by-product of carbon dioxide and has a high environmental load.

  In order to solve the problem of the Haber-Bosch method, a method of obtaining hydrogen by a water splitting reaction has been proposed (see Patent Document 3). In the method according to this proposal, a heat medium is heated using solar heat energy, and a water splitting reaction is caused using the heat energy of the heat medium to obtain hydrogen. According to this method, there is an advantage that the environmental load can be reduced in using natural energy, and the collection load of high-temperature solar thermal energy can be reduced.

  The method of obtaining hydrogen by the water splitting reaction as described above is a method that does not generate carbon dioxide and has a low environmental load, and is more advantageous than the Haber-Bosch method. However, not only is the energy required to decompose water to obtain hydrogen, but also the energy required for the reaction between the obtained hydrogen and nitrogen large, and in addition to requiring a catalyst for ammonia synthesis. Therefore, improvement in cost is desired.

JP 2013-158706 A JP 2013-154145 A JP 2013-241303 A

  The present invention has been made in view of such circumstances, and has a highly efficient method for producing a reaction product using a phase interface reaction in which a plasma-like substance (ozone, nitrogen plasma, or the like) reacts with water and the like, and a phase used therein. An object of the present invention is to provide an interfacial reaction device and a secondary reaction product production method for producing a secondary reaction product using a reaction product.

  According to the first aspect of the present invention, there is provided a reaction product manufacturing method using a phase interface reaction according to the first aspect, wherein a plasma supply step of supplying a plasma-like substance into a reaction vessel, and water or an aqueous solution is supplied into the reaction vessel. Water / aqueous solution supply step, and an ultraviolet irradiation step of irradiating the plasma-like substance in the reaction vessel with ultraviolet light, and the plasma-like substance and the water or the aqueous solution are contained in the reaction vessel. This is a method of producing a reaction product by reacting a solute with a phase interface.

According to the reaction product manufacturing method using the phase interface reaction according to the first invention, at the phase interface between the plasma phase and the liquid phase in contact with the plasma phase, the plasma-like substance and the solute contained in the water or the aqueous solution , The contact area between the two components is large and the reaction can be performed with high efficiency. At this time, a reaction between the plasma substance and gaseous water (water vapor) also occurs. Further, plasma can be generated in a place different from the reaction field (in the reaction vessel) having a certain degree of humidity, and plasma can be supplied to the reaction field, so that the plasma generation efficiency does not decrease. In the present application, "plasma" refers to particles in which gas or gaseous, positively charged particles and negatively charged electrons are distributed while maintaining almost electrical neutrality, regardless of the generation method. A group, or a group in which the particle group and an atomic or molecular gas are mixed. For this reason, in the present application, the term "plasma state" refers to a state in which some or all of the molecules constituting a gas are ionized or dissociated, or a state in which dissociated atoms are associated, and a state in which these are present in a mixed state. . Specifically, the ionized state is a state of ions and electrons, the dissociated state is a state existing as oxygen atoms, nitrogen atoms, and the like, and the state where atoms are associated is ozone (O ₃ ) and the like. It exists. For example, plasma-like oxygen (oxygen plasma) is usually a mixture of ozone (O ₃ ), oxygen molecules (O ₂ ), oxygen atoms (O), and the like. Nitrogen (N) occupies most of plasma-like nitrogen (nitrogen plasma). The “plasma-like substance” may be a gaseous ultraviolet-reactive substance such as ozone or nitrogen atom.

  Furthermore, in the method for producing a reaction product using a phase interface reaction according to the first invention, a plasma supply step of supplying a plasma-like substance into the reaction vessel, and mist water or an aqueous solution is supplied into the reaction vessel. An atomizing step of generating, and an ultraviolet irradiation step of irradiating the plasma-like substance in the reaction vessel with ultraviolet rays in a state where the humidity (relative humidity) in the reaction vessel is less than 100%, It is preferable that the plasma-like substance and the solute contained in the mist-like water or the mist-like aqueous solution are reacted at a phase interface in a container. By setting the humidity in the reaction vessel to less than 100%, it is possible to suppress the dominant ultraviolet absorption of water molecules, and the reaction can proceed efficiently. By setting the humidity to less than 100%, the reaction product can be efficiently recovered in a gaseous state. When the humidity is 100%, a large amount of dew (water droplets) is formed on the inner surface of the reaction vessel, and the amount of the water-soluble reaction product dissolved in the water droplets increases. Therefore, it is necessary to collect both gas and liquid.

  In the method for producing a reaction product using a phase interface reaction according to the first invention, it is preferable that the humidity in the reaction vessel at the time of the ultraviolet irradiation step is 40% or more and 70% or less. By setting the humidity within the above range, the reaction efficiency can be further increased.

  In the method for producing a reaction product using a phase interface reaction according to the first invention, it is preferable that the atomization step is performed by heating the water or the aqueous solution in the reaction vessel. By generating the mist by heating, it becomes easy to control the humidity, the particle size of the mist, and the like to a favorable state. Further, by atomizing water or the like in the reaction vessel, it is possible to irradiate all generated mist and water vapor with ultraviolet rays, which is efficient. Further, by heating in the reaction vessel, as a result, the temperature in the reaction vessel increases, and the amount of saturated steam increases. That is, since the amount of water vapor present in the reaction vessel can be increased, the reaction efficiency can be further improved.

In the method for producing a reaction product using a phase interface reaction according to the first invention, it is preferable that the substance contains at least one selected from the group consisting of oxygen, nitrogen and carbon oxide (carbon dioxide, carbon monoxide). . Hydroxy radicals, singlet oxygen, and the like can be generated by using oxygen plasma (ozone), and ammonia can be synthesized by using nitrogen plasma. Further, hydrogen (H ₂ ) can be generated by decomposing this ammonia. In addition, the use of carbon oxide plasma enables the synthesis of organic substances such as hydrocarbons and alcohols.

  In the method for producing a reaction product using a phase interface reaction according to the first invention, it is preferable that the substance contains nitrogen and further comprises a decomposition reaction step of decomposing ammonia generated by the reaction at the phase interface. By doing so, hydrogen molecules can be obtained.

  A phase interface reaction apparatus according to a second aspect of the present invention, which meets the above object, comprises a reaction vessel, plasma supply means for supplying a plasma-like substance into the reaction vessel, and water for supplying water or an aqueous solution into the reaction vessel. An aqueous solution supply means, and an ultraviolet irradiation means for irradiating the plasma-like substance in the reaction vessel with ultraviolet light, wherein the plasma-like substance and the solute contained in the water or the aqueous solution in the reaction vessel are This is a device that reacts at the phase interface.

  In the phase interface reaction apparatus according to the second invention, the water / aqueous solution supply means is atomization means for generating mist-like water or an aqueous solution in the reaction vessel so as to be able to control the humidity, and comprises: Plasma supply means for supplying a plasma-like substance into a vessel, the atomization means, comprising the ultraviolet irradiation means, the plasma-like substance and the mist-like water or the mist-like water in the reaction vessel The solute contained in the aqueous solution can be reacted at the phase interface.

  According to the phase interface reaction device according to the second aspect of the present invention, a plasma substance and a solute contained in water or an aqueous solution are reacted at a phase interface between a plasma phase and a liquid phase in contact with the plasma phase. To carry out the reaction.

  In the phase interface reaction device according to the second invention, it is preferable that the atomizing means is a heater for the water or the aqueous solution, and the heater is disposed in the reaction vessel. By generating mist by heating water or the like using a heater, it becomes easy to control the humidity, the particle size of the mist, and the like in a favorable state. Further, the temperature in the reaction vessel can be increased by the heater, the amount of saturated steam can be increased, and the amount of steam in the reaction vessel can be increased.

  A method for producing a secondary reaction product according to a third aspect of the present invention is a method for producing a secondary reaction product by reacting a reaction product generated by the above-described phase interface reaction with another substance.

  In the method for producing a secondary reaction product according to the third invention, the reaction product generated by the phase interface reaction may include active oxygen or a hydroxyl radical.

  Further, in the phase interface reaction device according to the second invention, a reaction product generated by a phase interface reaction between the plasma substance and a solute contained in the water or the aqueous solution in the reaction vessel or outside thereof is provided. It can be reacted with another substance to produce a secondary reaction product.

  By using such a secondary reaction product production method or a phase interface reaction apparatus for performing the same, a new reaction product obtained by applying the reaction product obtained by the phase interface reaction at normal temperature, normal pressure, and no catalyst is used. A reaction method can be constructed. In particular, a new organic synthesis or a new metal surface treatment can be realized by reacting the above reaction product with another substance (for example, an organic compound or metal). When the reaction product contains active oxygen or a hydroxyl radical, oxidation of the organic compound can be performed by the reaction between the reaction product and the organic compound, and oxidation of the metal surface by the reaction between the reaction product and the metal. It can be performed.

  ADVANTAGE OF THE INVENTION According to the reaction product manufacturing method using the phase interface reaction according to the first invention, and the phase interface reaction device according to the second invention, a plasma-like substance can be reacted with water and the like with high efficiency. Further, according to the method for producing a secondary reaction product according to the third invention, a new synthesis or surface treatment can be realized using the reaction product obtained by the phase interface reaction. Therefore, the present invention can enhance the productivity of various chemical syntheses and the like, material processing (anticorrosion processing, modification, etc.), sanitary technology (sterilization, dust removal, virus removal, etc.), and renewable energy (hydrogen purification). Etc.) can be used in various fields such as fields.

1 is a schematic diagram illustrating a phase interface reaction device according to an embodiment of the present invention. FIG. 2 shows another embodiment of the phase interface reaction apparatus of FIG. FIG. 3 schematically shows a typical mode of a phase interface reaction between a plasma substance and water or an aqueous solution. 4A is an ESR spectrum of DMPO-OH in a 0.3 M DMPO aqueous solution (ozone supply amount 4 L / min × 10 min, ultraviolet irradiation time 10 min), and FIG. ^TPC-1 O ₂ of the ESR spectrum in TPC aqueous solution (ozone supply amount 4L / min × 10min, UV irradiation time 10min) is. Figure 5 is a graph showing the relationship between the ^TPC-1 O ₂ produced a UV irradiation time (ozone supply amount 4L / min × 2min). Figure 6 is a graph showing the relationship between the ^TPC-1 O ₂ generated ozone supply amount (ozone feed rate 4L / min, UV irradiation time 1min). Figure 7 is a graph showing the relationship between the humidity and the generated ^TPC-1 the amount of O _2. FIG. 8 shows a comparison of the amount of ammonia produced by three types of systems, “N plasma phase / water phase + UV irradiation”, “N ₂ gas phase / water phase + UV irradiation”, and “N plasma phase / water phase”. . FIG. 9 shows NMR spectra of indole before and after treatment with active oxygen generated by a phase interface reaction. FIG. 10 shows an ATR total reflection FTIR spectrum of a copper plate surface treated with active oxygen generated by a phase interface reaction.

10: phase interface reactor, 11: reaction vessel, 12: plasma generator (one example of plasma supply means), 13: heater (one example of water / aqueous solution supply means, one example of atomization means), 14: UV lamp ( Example of ultraviolet irradiation means), 15: plasma supply port, 16: supply port, 17: discharge port, 18: pipe, 19: heated container (example of water / aqueous solution supply means), 20: diffusion fan, 21, 22 : Pipe, 30: shower device (an example of water / aqueous solution supply means), X: water or aqueous solution

Next, embodiments of the present invention will be described with reference to the accompanying drawings.
[Phase interface reactor]
As shown in FIG. 1, a phase interface reactor 10 according to one embodiment of the present invention includes a reaction vessel 11, a plasma generator 12 as an example of plasma supply means, a heater 13 as an example of atomization means, And a UV lamp 14 as an example of an ultraviolet irradiation means.

  The reaction vessel 11 is for reacting a plasma-like substance with atomized water or the like inside the reaction vessel 11. The reaction container 11 may be a known container, may be a transparent container made of glass or the like, or may be an opaque container made of ceramics or the like. At the bottom of the reaction vessel 11, a plasma supply port 15, a supply port 16 for other gas and the like, and a discharge port 17 are provided.

  The plasma generator 12 is a device that generates plasma of a substance to be reacted and supplies the generated plasma (plasma-like substance) into the reaction vessel 11. As the plasma generation device 12, a known plasma generation device such as a device using an electric discharge such as an arc discharge, a device using a high-frequency electromagnetic field, and a device using a microwave can be appropriately used. When the substance to be reacted is oxygen, a known ozone generator can be used as the plasma generator 12. The plasma generator 12 and the reaction vessel 11 are connected by a pipe 18. That is, the plasma generated by the plasma generator 12 is supplied from the plasma supply port 15 to the reaction vessel 11 through the pipe 18.

  The heater 13 is preferably installed on the bottom surface inside the reaction vessel 11. A heated container 19 containing water (or aqueous solution) X is placed on the heater 13. The heated container 19 is an example of a water / aqueous solution supply unit that supplies water or an aqueous solution into the reaction container 11 and does not necessarily need to be heated. Therefore, when heating is not required, the container 19 to be heated can be simply referred to as a “container”. The heater 13 heats the heated container 19 and the water X therein. By this heating, the water X in the heated container 19 is volatilized, and mist-like water is generated in the reaction container 11. The heater 13 is not particularly limited as long as it can heat the container 19 to be heated and the water in the container 19 to be heated. In addition to the electric heater, a gas heater, a high-frequency induction heating device, or the like can be used.

  The heater 13 generates a mist so that the humidity in the reaction vessel 11 can be controlled. This humidity control can be performed by controlling the heating temperature (the amount of heat applied to the water X). That is, by heating at a high temperature, the amount of volatilization can be increased and the humidity can be increased. Conversely, by heating at a low temperature, the amount of volatilization can be reduced and the humidity can be reduced. In addition, since the heater 13 and the container 19 to be heated are installed in the reaction container 11, the temperature in the reaction container 11 increases due to the heating of the heater 13. Therefore, the amount of water (water vapor and mist) that can be present in the air can be increased by increasing the amount of saturated vapor in the reaction vessel 11 by the heater 13. That is, the heater 13 increases both the amount of steam and the amount of saturated steam, and the humidity is determined from these. Note that the control of the heating temperature is performed by controlling the amount of power when the heater 13 is an electric heater, for example.

  The UV lamp 14 is disposed above the inside of the reaction vessel 11. The UV lamp 14 irradiates the plasma-like substance supplied from the plasma generator 12 into the reaction vessel 11 with ultraviolet rays. At this time, the UV lamp 14 further irradiates the mist water and the water X in the heated container 19 with ultraviolet rays. The wavelength of the ultraviolet light emitted by the UV lamp 14 is appropriately set according to the type of the reactant and the like. For example, when the reactant is oxygen (ozone), the wavelength can be set to 185 nm and 254 nm. The output of the UV lamp 14 is not particularly limited, and may be, for example, 0.1 to 100 W.

  A diffusion fan 20 is further provided in the reaction vessel 11. The diffusion fan 20 diffuses the plasma-like substance and the mist-like water into the reaction vessel 11. A pipe 21 is connected to the supply port 16 of the reaction vessel 11 so that a reaction target gas or the like can be supplied from a pump or the like (not shown). Further, a pipe 22 is connected to the outlet 17 of the reaction vessel 11 so that generated gas and unreacted gas are discharged. The plasma supply port 15, the supply port 16, and the discharge port 17 can each be configured to be openable and closable.

  In the phase interface reactor 10, the plasma-like substance and the mist-like water react in the reaction vessel 11 at the phase interface between the plasma phase and the liquid phase dispersed in the mist state in the plasma phase. . Note that gaseous water (steam) in a volatile state may also react. This reaction will be described later as a method for using the phase interface reaction apparatus 10 and a method for producing a reaction product using the phase interface reaction.

  FIG. 2 shows another embodiment of the phase interface reaction apparatus of FIG.

  As shown in FIG. 2, a phase interface reactor 10 according to another embodiment of the present invention includes a reaction vessel 11, a plasma generator 12 as an example of a plasma supply unit, and a UV lamp 14 as an example of an ultraviolet irradiation unit. And a shower device 30 which is an example of a water / aqueous solution supply means. The phase interface reaction device 10 of FIG. 2 is different from the phase interface reaction device 10 of FIG. 1 in that a shower device 30 is provided instead of the heater 13, the container 19 to be heated, and the diffusion fan 20. In common with the phase interface reactor 10 of FIG. Therefore, the description of the common configuration will be omitted instead of the above description. Note that the diffusion fan 20 may be provided in the phase interface reaction device 10 of FIG.

  The shower device 30 has a pipe 31 penetrated into the reaction vessel 11, and has a shower head 32 at its tip. The shower head 32 has a porous surface 33 having a number of small holes on its lower surface. When water or an aqueous solution containing a solute is supplied into the reaction vessel 11 from the porous surface 33 of the shower head 32, it reacts at the phase interface with a plasma-like substance separately supplied into the reaction vessel 11.

  FIG. 3 schematically shows a typical mode of a phase interface reaction between a plasma substance and water or an aqueous solution (hereinafter, referred to as “water”). The plasma-like substance may be of any type represented by oxygen plasma, nitrogen plasma, air plasma and the like.

Each mode shown in FIG. 3 is as follows.
(A) Flat water phase (a type of flat interface)
The plasma-like substance reacts on the surface of the water contained in the container.
(B) Inclined flat water phase (a type of flat interface)
The plasma-like substance reacts on the surface of the water flowing on the inclined surface.
(C) Dispersed Aqueous Phase The plasma-like substance reacts on the surface of water vapor dispersed in a mist state in the container.
(D) Dropped Water Phase The plasma-like substance reacts on the surface of a water drop dropped into the container.
(E) Aqueous phase The plasma-like substance is bubbled into water filling the container or water in a water tank placed in the container, and reacts with water on the surface of the foam.

  As described above, the aspect of the aqueous phase / plasma phase interface includes a flat interface ((A) and (B)), a dispersed aqueous phase (C), a dripped aqueous phase (D), and an aqueous phase (E). Although any phase interface can be a reaction field, the irradiation efficiency of ultraviolet rays for improving the reaction efficiency and the exchange of protons at the water interface depend on the plasma / water phase interface (A), (B), (C). And (D) are preferred.

  The phase interface reaction device 10 in FIG. 1 corresponds to (C) in the form of the aqueous phase / plasma phase interface shown in FIG. 3, and atomizes water or an aqueous solution in the reaction vessel 11 so as to control the humidity. As means, a heater 13 is preferably provided. However, the heater 13 is not an essential component for the phase interface reaction device 10, and may include only the shower device 30 as in the phase interface reaction device 10 of FIG. In that case, the state of the aqueous phase / plasma phase interface corresponds to (D) in FIG.

  Further, the phase interface reactor 10 of FIG. 1 may include only the container 19 to be heated, and the surface of the water in the container 19 to be reacted with a plasma-like substance (such as ozone or nitrogen plasma). In that case, the state of the aqueous phase / plasma phase interface corresponds to (A) in FIG. Further, an inclined plate may be arranged inside the reaction vessel 11 without disposing the vessel 19 to be heated inside the reaction vessel 11. Water flowing through the surface of the inclined plate by pumping water in the container to be heated 19 up to the upper side of the inclined plate by the pump, and returning the water dropped below the surface of the inclined plate to the container 19 to be heated, You may make it react with the plasma-like substance which contacts the surface. In this case, the state of the aqueous phase / plasma phase interface corresponds to (B) in FIG.

  Further, a glass-made bubbling device containing water is arranged in the reaction vessel 11, a plasma-like substance is supplied into the bubbling apparatus to perform bubbling, and water and a plasma-like substance are generated on the surface of the generated bubbles. May be caused. In that case, the state of the aqueous phase / plasma phase interface corresponds to (E) in FIG.

[Method for producing reaction product using phase interface reaction]
The method of using the phase interface reaction apparatus 10 (the method of producing a reaction product using a phase interface reaction) includes a plasma supply step of supplying a plasma-like substance into the reaction vessel 11, and water or an aqueous solution in the reaction vessel 11. A water / aqueous solution supply step for supplying, and an ultraviolet irradiation step of irradiating the plasma-like substance in the reaction vessel 11 with ultraviolet rays, wherein the plasma-like substance and the solute contained in the water or the aqueous solution are contained in the reaction vessel 11. The reaction is performed at the phase interface.

  In addition, a reaction product manufacturing method using a phase interface reaction (hereinafter, also referred to as “reaction product manufacturing method” as appropriate) includes the above-described water / aqueous solution supply step in which mist water or an aqueous solution is placed in the reaction vessel 11. As the atomization step to be generated, the ultraviolet irradiation step may be a step of irradiating the plasma-like substance in the reaction vessel 11 with ultraviolet rays in a state where the humidity in the reaction vessel is less than 100%. The order of the plasma supply step, the atomization step, and the ultraviolet irradiation step is not particularly limited as long as a phase interface reaction occurs. Usually, these steps are performed simultaneously, or at least the atomization step and the ultraviolet irradiation step are performed simultaneously. Is preferred.

(Plasma supply process)
In the plasma supply step, a plasma-like substance is supplied into the reaction vessel 11 by operating the plasma generator 12. Here, when oxygen gas (oxygen molecules) is supplied to the plasma generator 12, ozone (O ₃ ) and oxygen atoms (O), and other oxygen molecules, ionized ions and electrons are converted to oxygen plasma (plasma-like oxygen). Is supplied to the reaction vessel 11 through the pipe 18. When nitrogen gas (nitrogen molecules) is supplied to the plasma generator 12, a mixture of nitrogen atoms (N), other nitrogen molecules, ionized ions and electrons is supplied to the reaction vessel 11 as nitrogen plasma (plasma-like nitrogen). You. When carbon dioxide is supplied to the plasma generator 12, a mixture of carbon monoxide, carbon atoms, oxygen atoms, carbon dioxide, and other ions and electrons is supplied to the reaction vessel 11 as carbon oxide plasma (plasma-like carbon oxide). Supplied. The substance supplied to the reaction vessel 11 in the plasma state is not limited to these inorganic substances, and may be other organic substances (hydrocarbon, alcohol, ammonia, etc.). Furthermore, only one kind of substance may be turned into plasma, or a mixture of two or more kinds of substances (for example, air or the like) may be turned into plasma and supplied to the reaction vessel 11.

  The supply rate of the plasma-like substance to the reaction vessel 11 is not particularly limited, and is appropriately set according to the size of the apparatus and the like, but can be, for example, about 0.1 L / min to about 100 L / min.

(Water / aqueous solution supply process)
In the water / aqueous solution supply step, water or an aqueous solution to be brought into contact with the plasma-like substance supplied from the plasma generator 12 is supplied into the reaction vessel 11. As described with reference to FIG. 3, the supply method includes various methods, and is not particularly limited. For example, when the water / aqueous solution supply step is an atomization step of generating atomized water or an aqueous solution in the reaction vessel 11, the following steps are performed.

(Atomization process)
In the atomization process, the heater 13 is operated to generate mist (mist water or mist aqueous solution) in the reaction vessel 11. That is, the water (or aqueous solution) X in the container 19 to be heated rises in temperature by the heater 13, volatilizes and solidifies, and becomes fine droplets dispersed in the air. The heating temperature of the heater 13 (room temperature in the reaction vessel 11) is not particularly limited, but is preferably 30 ° C or more and 50 ° C or less, and more preferably 35 ° C or more and 45 ° C or less. By heating in the above temperature range, fog suitable for the phase interface reaction can be generated. If the temperature is too high, the mist particles may expand and the reaction efficiency may decrease, or the amount of volatilization exceeding the increase in the amount of saturated water vapor may occur, and the humidity may reach 100% and a large amount of dew may occur.

  In addition to the pure water, a solute aqueous solution can be heated to generate a mist-like aqueous solution. The solute is not particularly limited as long as it has water solubility and reacts with plasma. For example, organic substances such as alcohols and carboxylic acids may be used, and inorganic substances such as ammonia and metal salts may be used. Further, it may be an electrolyte or a non-electrolyte. When the boiling point of the solute in the aqueous solution largely deviates from that of water, the concentration of the solute contained in the mist decreases, but a certain amount of the solute is contained in the mist.

(UV irradiation step)
In the ultraviolet irradiation step, the plasma-like substance in the reaction vessel 11 supplied from the plasma generator 12 is irradiated with ultraviolet light. Ultraviolet light is emitted by a UV lamp 14. This ultraviolet irradiation is preferably performed in a state where the humidity (relative humidity) in the reaction vessel 11 is less than 100%. When the humidity is 100%, the reaction efficiency is low due to, for example, dominant ultraviolet absorption of water molecules present in a large amount in the reaction field (in the air, on a wall surface, etc.). Further, by performing the reaction under the condition of unsaturated steam, all the reaction products can be basically taken out in a gaseous state. The humidity in the reaction vessel 11 at the time of this ultraviolet irradiation is preferably from 40% to 70%, more preferably from 45% to 65%. If the humidity is too low, the amount of water dispersed and present in the reaction field (air in the reaction vessel 11) decreases, and the amount of generated water decreases. If the humidity is too high, the amount of ultraviolet light absorbed by water tends to increase, and even if the humidity does not reach 100%, a large amount of dew condensation tends to occur locally. The duration of the ultraviolet irradiation is not particularly limited, and is appropriately set according to the plasma, the amount of moisture, and the like. The irradiation time can be, for example, 0.1 minute or more and 30 minutes or less.

  Irradiation of ultraviolet rays causes a reaction between the plasma-like substance and water (or a solute contained in the aqueous solution), preferably mist-like water (or a solute contained in the mist-like aqueous solution) in the reaction vessel 11 at the phase interface. As described above, at the phase interface between the plasma phase and the liquid phase in contact with the plasma phase, the plasma-like substance reacts with the solute contained in the water or the aqueous solution. It can be performed.

When plasma oxygen (so-called oxygen plasma including ozone) is used as the plasma substance, the following reaction proceeds.
O ₃ + hν (UV) → ³ O ₂ + O (1)
O + H ₂ O + hν (UV) → 2HO · (2)
³ O ₂ + HO ・ → HOOO ・ (3)
HOOO ・ + hν (UV) → ¹ O ₂ + HO ・ (4)
That is, hydroxy radicals (OH radicals) are generated by the reactions (1) and (2) described in the background art, and singlet oxygen is further generated by the reactions (3) and (4). Hydroxy radicals and singlet oxygen are examples of reaction products generated by a phase interface reaction.

  Here, a reactant for reacting with the generated hydroxyl radical or singlet oxygen can be supplied into the reaction vessel 11 from the supply port 16 through, for example, the pipe 21. The reactant may be a gas (eg, nitrogen, methane, etc.) or a liquid. In the case of a liquid, it can be supplied in the form of a mist. Alternatively, the reactant may be present in the reaction vessel 11 from the beginning.

  Hydroxy radical, singlet oxygen, or a reaction product obtained by further reacting these can be recovered from the pipe 22 through the outlet 17, for example. Further, when the reaction product is water-soluble, the reaction product may be recovered from the water in the heated container 19 because it is dissolved in the water in the heated container 19.

  When plasma-like nitrogen is used as the plasma-like substance, nitrogen atoms (plasma) react with water at a phase interface by irradiation of ultraviolet rays, and ammonia and the like are generated. Ammonia is an example of a reaction product generated by a phase interface reaction. Here, when the further generated ammonia is supplied to the plasma generator 12 (discharge device), it is decomposed to obtain hydrogen molecules (and nitrogen molecules) (decomposition reaction step). Thus, hydrogen molecules can be obtained from nitrogen (air) and water as raw materials via ammonia.

  The method of synthesizing ammonia using the phase interface reaction is based on the phenomenon that the atomic gas generated in the plasma efficiently dissociates protons at the phase interface with water (plasma / water phase interface). This is a synthesis method using air or nitrogen and water as raw materials. When nitrogen molecules are passed through the discharge space of the plasma generator 12, the nitrogen is turned into plasma. When the phase interface between the nitrogen plasma and water is quickly formed, ammonia is generated. Irradiation of ultraviolet light to the nitrogen plasma / water phase interface to impart reaction energy further improves the efficiency of ammonia synthesis.

Ammonia is a gas at normal pressure, water solubility is very high (at _{20 ℃, NH 3 702g / H} 2 O 100g). For this reason, the synthesized ammonia is dissolved in the aqueous phase (partly exists in the atmosphere as a gas depending on the reaction system conditions). Therefore, the synthesized ammonia can be easily recovered by dissolving the aqueous phase. Further, since the dissolution rate is greatly reduced at a high temperature (eg, the dissolution rate is 1/8 at 100 ° C.), it is easy to recover as a gas depending on the reaction system conditions.

  Although the well-known Haber-Bosch method synthesizes ammonia in a high-temperature, high-pressure, catalyst system, the above-described phase interface reaction can proceed at room temperature, normal pressure, and no catalyst. Therefore, it is extremely advantageous in that the synthesis reaction of ammonia can be advanced with a small amount of energy input. This technology can procure raw materials anywhere (no transportation required), can synthesize ammonia using air and water as raw materials, extremely low raw material costs, does not generate carbon dioxide, has a low environmental load, and has low carbon dioxide transportation costs. Is unnecessary, the equipment is light-weight at normal temperature and normal pressure, low energy reaction system (non-equilibrium chemical reaction system at the phase interface), there is no need to generate hydrogen from hydrocarbon fuel Therefore, it has a great advantage in that energy costs can be significantly reduced. When ammonia is synthesized from air and water, since oxygen is present in the air, nitrogen plasma and oxygen plasma react with each other, and a small amount of NO is generated in the gas phase. However, NO is not dissolved in the aqueous phase at all, and can be easily exhausted as a gas. Therefore, it is considered that NO does not mix with ammonia in the liquid phase. It is considered that the fact that the water solubility of NO is remarkably lower than that of ammonia is one of the reasons that ammonia can be produced cheaply and safely.

  When plasma-like carbon oxide (carbon monoxide, carbon dioxide) is used as the plasma-like substance, organic substances such as hydrocarbons and alcohols can be synthesized by reaction with water or the like. Note that a plurality of substances, for example, nitrogen and oxygen (air) may be used as plasma. The phase interface reaction may be performed in a continuous manner or in a batch manner.

  The present invention is not limited to the above-described embodiment, and its configuration can be changed without changing the gist of the present invention. For example, in the atomization step, mist may be sent into the reaction vessel 11 from outside the reaction vessel 11. As the atomizing means, in addition to the heater 13, an ultrasonic wave (ultrasonic humidifier) or other sprays that physically generate mist can be used. Furthermore, the ultraviolet irradiation means (UV lamp 14) can be installed outside the reaction vessel 11 and irradiate from outside. As the ultraviolet irradiation means, instead of or in combination with the UV lamp 14, an energy input means using light or an electromagnetic wave such as an excimer lamp (for example, a lamp that emits vacuum ultraviolet light of 180 nm or less) may be used. .

[Secondary reaction product production method]
The secondary reaction product production method is a method of producing a secondary reaction product by reacting a reaction product generated by the above-described phase interface reaction with another substance. Here, the reaction product means a hydroxy radical, singlet oxygen (a kind of active oxygen) or the like when a phase interface reaction between oxygen plasma and water is performed. Further, for example, when a phase interface reaction between nitrogen plasma and water is performed, a reaction product means ammonia. The phase interface reaction is performed by the above-mentioned (A) plain water phase (one kind of flat interface), (B) inclined flat water phase (one kind of flat interface), (C) dispersed water phase, (D) dripped water phase, or (E) water. It may be performed in any of the phases (see FIG. 3). The other substance is not particularly limited as long as it can react with the above reaction product. Another substance includes, for example, an organic compound or an inorganic compound (including a metal). When the reaction product has a property of oxidizing another substance such as active oxygen, the other substance may be referred to as an oxygenation compound or an oxygenation substance.

  A reaction product (hydroxy radical, singlet oxygen, or the like) obtained by a phase interface reaction between oxygen plasma and water is an active substance having high electron withdrawing activity. Therefore, by reacting the reaction product with an organic compound (for example, indole), the organic compound can be oxidized in a short time. Indole may be dispersed or dissolved in a solvent. For example, when water is used as the solvent, it is preferable to prepare an aqueous solution containing 1 to 5% by weight of indole. When an organic solvent such as ethanol is used as the solvent, it is preferable to prepare a solution containing 10 to 30% by weight of indole. However, the content of the indole is merely an example, and a solution having a content other than the above may be used. Since this reaction can be carried out at normal temperature, normal pressure and without a catalyst, it is effective as an inexpensive technique for organic synthesis. As another substance that reacts with the reaction product generated by the phase interface reaction, a substance other than indole may be used. Flavones, quercetin, catechin, pyrrole, styrene, thiophene, benzaldehyde, indene, and the like can be used.

  Further, by reacting a reaction product with a metal (for example, copper or the like), the surface of the metal can be oxidized in a short time. Since this reaction can also be carried out at normal temperature, normal pressure and without a catalyst, it is effective as an inexpensive metal surface treatment technique. The metal may be other than copper, and for example, iron, nickel, and zinc can be used.

  The method for producing a secondary reaction product can be performed inside or outside the above-described phase interface reactor 10. When producing a secondary reaction product outside the phase interface reaction device 10, another reaction device connected by a pipe from the phase interface reaction device 10 is prepared, and the reaction product obtained by the phase interface reaction method is prepared. Is drawn into the other reactor through the above-mentioned piping, and is brought into contact with another substance (for example, an organic compound, a metal, or the like) disposed inside the another reactor.

  On the other hand, when a secondary reaction product is produced inside the phase interface reaction device 10, an organic compound or a liquid containing an organic compound mixed with a predetermined solvent (such as water) is placed in a reaction vessel 11 of the same device 10. It is preferable that the reaction product generated in the apparatus 10 is put in a container such as a petri dish and the organic compound is brought into contact with the reaction product. When an organic compound is dispersed or dissolved in water and placed in a container such as a Petri dish, it is preferable to prepare a heated container 19 in which water reacting with the plasma-like substance is placed in a container separate from the Petri dish. However, only a petri dish containing water in which an organic compound is dispersed or dissolved is put into the reaction vessel 11, and a reaction product obtained by reacting the water in the petri dish with a plasma-like substance, and an organic compound in the petri dish To produce a secondary reaction product. When reacting a reaction product with a metal, the metal is preferably placed in the reaction vessel 11 of the apparatus 10 and the reaction product generated in the reaction vessel 11 is preferably brought into contact with the metal. The form of the metal is not limited, such as a plate or a powder. When a plate-shaped metal is subjected to a surface treatment, it is preferable to arrange the plate-shaped metal in the reaction vessel 11. When performing the surface treatment of the metal powder, the powder is vibrated or agitated under an explosion-proof condition at a specific place in the reaction vessel 11, and the reaction product and the metal powder are preferably brought into contact with the specific place. .

  As described above, in the phase interface reaction device 10, the reaction product generated by the phase interface reaction between the plasma-like substance and the solute contained in the water or the aqueous solution in the reaction vessel 11 or outside thereof and another substance (for example, , An organic compound, a metal, etc.) to produce a secondary reaction product, whereby, for example, a new organic synthesis method or a metal surface treatment method can be constructed.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples. Note that the present invention is not limited to the following embodiments.

Example 1 Production of Hydroxyl Radical and Singlet Oxygen A phase interface reactor having the configuration shown in FIG. 1 was prepared. Two UV lamps having a wavelength of 185 nm and an output of 0.16 W and two lamps having a wavelength of 254 nm and an output of 1.6 W were used. In addition, a sample table for mounting a hole slide glass described later was set in the reaction vessel. The plasma generator (ozone generator) was discharged at 6 kV, oxygen plasma (ozone) was supplied to the reaction vessel, and a mist (fog water) was generated in the reaction vessel by a heater. The reactor was heated by a heater so that the temperature inside the reactor became 40 ° C. Further, the humidity in the reaction vessel was 50%. In this state, a UV lamp was irradiated.

The products, hydroxy radical and singlet oxygen, were observed by ESR-spin trapping. As a spin trapping agent, a 0.3 M aqueous solution (500 μL) of 5,5-dimethyl-1-pyrroline N-oxide (DMPO; Labotech) and 2,2,5,5-tetramethyl-3-pyrroline-3 Using a 0.5 M aqueous solution (500 μL) of carboxamide (TPC; Sigma-Aldrich), these were respectively dropped onto a hole slide glass, and mounted on a sample table in a reaction vessel. DMPO is a hydroxy radical, TPC will trap singlet oxygen, DMPO-OH respectively as spin adduct, the ^TPC-1 O _2. ESR was measured at room temperature using JEOL JFS-FA100.

After supplying oxygen plasma (ozone) at 4 L / min and irradiating ultraviolet rays for 10 minutes, the ESR spectrum of each spin trapping agent (spin adduct) was measured. The spectra are shown in FIGS. 4 (a) and 4 (b), respectively. The concentration of DMPO-OH obtained from these 9 × ¹⁰ -3 mM, the ^TPC-1 O ₂ concentration was 15mM and high concentration.

Next, the reaction was carried out in the same manner by changing the ultraviolet irradiation time (the supply amount of ozone was 4 L / min for 2 minutes). Then, to determine the concentration of the spin adduct (TPC- ¹ O ₂₎ as well. The results are shown in FIG. The abscissa of FIG. 5 indicates the UV irradiation time (UV irradiation time (min)), and the ordinate indicates the concentration of the spin adduct (Spin Adduct (TPC- ¹ O ₂ ) (mM)). It can be seen that the longer the ultraviolet irradiation time, the larger the amount of spin adduct (singlet oxygen) produced, and that ultraviolet irradiation promotes the production of singlet oxygen.

The same reaction was performed by changing the supply amount of oxygen plasma (ozone) (the supply rate of ozone was 4 L / min, and the irradiation time of ultraviolet rays was 1 minute). Then, to determine the concentration of the spin adduct (TPC- ¹ O ₂₎ as well. FIG. 6 shows the results. The horizontal axis in FIG. 6 indicates the ozone supply (introduced) volume (Introduced Ozone volume (L)), and the vertical axis indicates the concentration of the spin adduct (Spin Adduct (TPC- ¹ O ₂ ) (mM)). It can be seen that the larger the supply amount of ozone, the larger the generation amount of singlet oxygen (substantially in a proportional relationship). This is presumed to be because the chain reactions of the formulas (1) to (4) proceed in the reaction field.

Next, the same reaction was carried out while changing the humidity (relative humidity) in the reaction vessel. Then, the concentration was determined (generation amount) of similarly spin adduct ^(TPC-1 O _2). The results are shown in FIG. 7 as relative values when the humidity of 50% is taken as 100 (%). It can be seen that singlet oxygen is produced at a high concentration when the humidity is in the range of 40 to 70%, particularly when the humidity is 50% and 60%. In this embodiment, water (or aqueous solution) in the reaction atmosphere (space in the reaction vessel) may be present as a gas (water vapor) or may be present as a dispersed liquid (mist). Therefore, the humidity value cannot be said to be a value that completely reflects the amount of water in the atmosphere, but is also an index of the amount of water present.

<Example 2> Synthesis of ammonia As in Example 1, a phase interface reaction apparatus having the configuration shown in Fig. 1 was prepared. The same UV lamp as in Example 1 was used. Nitrogen gas (purity: 99.99% or more) was supplied to a plasma generator (for generating nitrogen plasma), discharged at a voltage of 6 kV, and nitrogen plasma was supplied into the reaction vessel. On the other hand, 20 ml of ultrapure water was placed in a petri dish having a diameter of 13 cm (aqueous phase surface area: 132 cm ² ), and mist (fog-like water) was generated in the reaction vessel by a heater. The reactor was heated by a heater so that the temperature inside the reactor became 40 ° C. Further, the humidity in the reaction vessel was 50%. In this state, the surface of the aqueous phase was irradiated with a UV lamp for 10 minutes. This system is referred to as "N plasma phase / water phase + UV irradiation". The amount of ammonia formed in the aqueous phase was determined by accurately coloring the petri dish aqueous phase by the "indophenol blue coloration method", measuring the absorbance thereof, and accurately quantifying the standard substance calibration method.

For comparison, a system “N ₂ gas phase / water phase + UV irradiation” in which nitrogen gas was supplied instead of the nitrogen plasma of “N plasma phase / water phase + UV irradiation” and “N plasma phase / water phase + UV irradiation” The system was also subjected to both UV irradiation and the "N plasma phase / aqueous phase" to determine the amount of ammonia produced.

FIG. 8 shows a comparison of the amount of ammonia produced by three types of systems, “N plasma phase / water phase + UV irradiation”, “N ₂ gas phase / water phase + UV irradiation”, and “N plasma phase / water phase”. . As is clear from FIG. 8, in the “N plasma phase / water phase + UV irradiation” system, generation of much more ammonia was confirmed than in the other two systems. This result indicates that, in the ammonia synthesis, a method in which nitrogen gas is brought into a plasma state and UV irradiation is performed in a contact environment with an aqueous phase is superior. The energy required for synthesizing 170 μg of ammonia in the right end bar graph of FIG. 8 is only the power of silent discharge for generating nitrogen plasma and the power of ultraviolet irradiation on the reaction interface, and the amount is extremely small, 5 Wh or less.

<Example 3> Oxidation treatment of organic compound As in Example 1, a phase interface reaction apparatus having the configuration shown in Fig. 1 was prepared. 20 ml of an aqueous solution of indole (aqueous solution containing 3% by weight of indole) was poured into a petri dish having a diameter of 13 cm (aqueous phase surface area: 132 cm ² ), and the petri dish was placed in the above-mentioned phase interface reactor. The petri dish in this experiment is a container different from the heated container heated by the heater. The same UV lamp as in Example 1 was used. The supply amount of oxygen plasma (ozone) was set to 4 L / min as in Example 1. Oxygen plasma (ozone) was generated under the conditions of a silent discharger voltage of 6 kV. A fog (fog of water) was generated in the reaction vessel by a heater, and the reaction vessel was heated by a heater so that the temperature in the reaction vessel was 40 ° C. Further, the humidity in the reaction vessel was 50%. In this state, UV irradiation was performed for 10 minutes using a UV lamp. The indole aqueous solution in the petri dish was continuously stirred using a stirrer.

  The generation of oxygen plasma was carried out in the form of (C) dispersed aqueous phase shown in FIG. The reaction field of indole is “oxygen plasma phase / dispersed aqueous phase / indole dissolved in water solvent”. (C) In the form of a dispersed aqueous phase, hydroxyl radicals and active oxygen (hereinafter collectively referred to as active oxygen) generated at the interface between the oxygen plasma phase and the aqueous phase oxidize indole in the aqueous indole solution. That is, two kinds of reactions occur in the phase interface reaction apparatus, namely, a reaction for generating active oxygen and a reaction between the generated active oxygen and indole. The change of the indole due to the reaction between the active oxygen and the indole was identified from the change in the nuclear magnetic resonance (NMR) spectrum.

  FIG. 9 shows NMR spectra of indole before and after treatment with active oxygen generated by a phase interface reaction.

  As shown in FIG. 9, an NMR spectrum specific to indole was observed before the treatment with active oxygen. After the treatment with active oxygen, an NMR spectrum unique to 2-Formylaminobenzaldehyde was observed. From this result, it is considered that indole was oxidized by active oxygen and changed to 2-formylaminobenzaldehyde by addition of oxygen or ring opening. The reaction method using active oxygen generated by the phase interface reaction can be a new method of organic synthesis because the oxidation of an organic compound can be realized at normal temperature, normal pressure, and without a catalyst.

Example 4 Metal Surface Oxidation Treatment As in Example 1, a phase interface reaction apparatus having the configuration shown in FIG. 1 was prepared. A 5 mm wide x 20 mm long x 0.5 mm thick pure copper plate (hereinafter, referred to as a copper plate), which has been previously polished, acid-treated, and cleaned by degreasing using an organic solvent, is placed in the above-mentioned phase interface reaction apparatus. I put it inside. The same UV lamp as in Example 1 was used. The supply amount of oxygen plasma (ozone) was set to 4 L / min as in Example 1. Oxygen plasma (ozone) was generated under the conditions of a silent discharger voltage of 6 kV. A fog (fog of water) was generated in the reaction vessel by a heater, and the reaction vessel was heated by a heater so that the temperature in the reaction vessel was 40 ° C. Further, the humidity in the reaction vessel was 50%. In this state, UV irradiation was performed for 5 minutes using a UV lamp.

  The generation of oxygen plasma was carried out in the form of (C) dispersed aqueous phase shown in FIG. The reaction field of the copper plate is “oxygen plasma phase / dispersed aqueous phase / copper plate”. (C) In the form of a dispersed aqueous phase, active oxygen oxidizes the surface of the copper plate. That is, two kinds of reactions occur in the phase interface reaction apparatus, namely, a reaction for generating active oxygen and a reaction between the generated active oxygen and copper. The reaction between active oxygen and copper was examined by infrared spectroscopy (ATR total reflection measurement).

  FIG. 10 shows an ATR total reflection FTIR spectrum of a copper plate surface treated with active oxygen generated by a phase interface reaction.

In the spectrum shown in FIG. 10, an infrared absorption maximum peculiar to the Cu ₂ O layer was recognized. This result indicates that a Cu ₂ O layer (a cuprous oxide layer) was formed on the surface of the copper plate. Since active oxygen and radicals have strong electron withdrawing activity, an oxide film (suboxide film or oxide film) can be formed on a metal surface in a short time. Further, since the sub-oxide film and the oxide film which are formed instantaneously are dense, the metal inside thereof can be protected from corrosion. Further, since the sub-oxide layer has an electric rectification effect, a semiconductor material can be constructed at low cost.

Claims (11)

A plasma supply step of supplying a plasma-like substance generated by supplying a nitrogen gas to a plasma generator into a reaction vessel,
In the reaction vessel, a water / aqueous solution supply step of supplying water or an aqueous solution,
An ultraviolet irradiation step of irradiating the plasma-like substance in the reaction vessel with ultraviolet light;
Has,
A method for producing a reaction product containing ammonia using a phase interface reaction in which the plasma-like substance and the solute contained in the water or the aqueous solution are reacted at the phase interface in the reaction vessel. The method for producing a reaction product using a phase interface reaction according to claim 1, wherein the water / aqueous solution supply step is an atomization step of generating atomized water or an aqueous solution in the reaction vessel,
The step of irradiating the ultraviolet light is a step of irradiating the plasma-like substance in the reaction container with ultraviolet light in a state in which the humidity in the reaction container is less than 100%, using a phase interface reaction. A method for producing a reaction product containing ammonia.   The method for producing a reaction product using a phase interface reaction according to claim 2, wherein the humidity in the reaction vessel at the time of the ultraviolet irradiation step is 40% or more and 70% or less. A method for producing a reaction product containing ammonia used.   The method for producing a reaction product using a phase interface reaction according to claim 2 or 3, wherein the atomization step is performed by heating the water or the aqueous solution in the reaction vessel. For producing a reaction product containing ammonia.   The method for producing a reaction product using a phase interface reaction according to any one of claims 1 to 4, wherein the ultraviolet irradiation step is a step of irradiating the water or the aqueous solution with ultraviolet rays. For producing a reaction product containing ammonia using a phase interface reaction.   The method for producing a reaction product using a phase interface reaction according to claim 5, further comprising a decomposition reaction step of decomposing ammonia generated by the reaction at the phase interface, wherein the ammonia using a phase interface reaction is further provided. A method for producing a reaction product comprising: A reaction vessel,
A plasma generator, a plasma supply unit that supplies a plasma-like substance generated by supplying a nitrogen gas to the plasma generator into the reaction vessel,
Water / aqueous solution supply means for supplying water or an aqueous solution into the reaction vessel,
UV irradiation means for irradiating the plasma-like substance in the reaction vessel with ultraviolet light,
With
A phase interface reaction apparatus for producing a reaction product containing ammonia by reacting the plasma-like substance with a solute contained in the water or the aqueous solution in the reaction vessel at a phase interface. The phase interface reaction device according to claim 7, wherein the water / aqueous solution supply means is atomization means for generating mist-like water or an aqueous solution in the reaction vessel so as to be capable of controlling humidity,
A phase interface reaction device, wherein the plasma substance and the solute contained in the atomized water or the aqueous solution are reacted at the phase interface in the reaction vessel.   9. The phase interface reaction device according to claim 8, wherein the ultraviolet irradiation means also irradiates the water or the aqueous solution with ultraviolet light.   A method for producing a secondary reaction product, comprising reacting a reaction product containing ammonia produced by the phase interface reaction according to any one of claims 1 to 6 with another substance to produce a secondary reaction product. The phase interface reaction device according to any one of claims 7 to 9, wherein the phase interface reaction device is formed by a phase interface reaction between the plasma-like substance and a solute contained in the water or the aqueous solution in or outside the reaction vessel. A phase interface reactor for producing a secondary reaction product by reacting the reaction product obtained with another substance.